Well I was at the library because my sister had a painting class there, and while waiting for her to finish up I decided to look and see if they had any Marvel stuff. To my surprise I found The Ultimate Guide to Spiderman and The Ultimate Guide to Hulk. Flipping through the pages it bios all their villains and allies, so I have started making the cards, from the earliest villain forward.
Appearing in The Amazing Spiderman #1, here is Chameleon, master of disguise.
Chameleon (info) - The first costumed Spiderman villain, Chameleon is a master of disguise who can take appearance of anyone he sees.